Packaging product comprising a laminate having a biomass-derived resin layer

Abstract

Provided is a packaging product comprising a laminate having a paper substrate and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing carbon-neutral polyethylene using biomass-derived ethylene. [Solution] The packaging product comprises a laminate 10, the laminate comprising a paper substrate 11 and a biomass polyolefin resin layer 12 located on one side of the paper substrate and made of a biomass polyolefin resin composition containing biomass-derived polyethylene formed by polymerizing a monomer containing biomass-derived ethylene, and a fossil fuel-derived polyolefin, the paper substrate and the biomass polyolefin resin layer being in contact with each other, and the packaging product being a laminated tube.

Description

[Technical Field]

[0001] The present invention relates to a packaging product comprising a laminate having a biomass-derived resin layer, and more particularly to a packaging product comprising a laminate having a paper substrate and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing biomass-derived polyethylene obtained by polymerizing monomers including biomass-derived ethylene. [Background technology]

[0002] In recent years, with the growing demand for a circular economy, there is a desire to move away from fossil fuels in the materials sector, just as there is a desire for energy, and the use of biomass is attracting attention. Biomass is an organic compound produced through photosynthesis from carbon dioxide and water, and by utilizing it, it can be converted back into carbon dioxide and water, making it a so-called carbon-neutral renewable energy source. Recently, the practical application of biomass plastics made from these biomass materials has been progressing rapidly, and attempts are also being made to manufacture various resins from biomass raw materials.

[0003] While polylactic acid (PLA), produced via lactic acid fermentation, was the first biomass-derived resin to begin commercial production, its performance as a plastic differs significantly from current general-purpose plastics, particularly in its biodegradability. This has limited its product applications and manufacturing methods, preventing widespread adoption. Furthermore, life cycle assessments (LCA) have been conducted on PLA, and discussions are underway regarding its energy consumption during production and its equivalence as a substitute for general-purpose plastics.

[0004] Various types of general-purpose plastics are used here, including polyethylene, polypropylene, polyvinyl chloride, and polystyrene. In particular, polyethylene is molded into films, sheets, bottles, etc., and is used in a wide range of applications such as packaging materials, and is used in large quantities worldwide. Therefore, using conventional polyethylene derived from fossil fuels has a significant environmental impact.

[0005] Therefore, there is a desire to reduce the use of fossil fuels by using biomass-derived raw materials in the production of polyethylene. For example, research has been conducted to date on producing ethylene and butylene, which are raw materials for polyolefin resins, from renewable natural raw materials (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Special Publication No. 2011-506628 [Overview of the project] [Problems that the invention aims to solve]

[0007] The inventors focused on ethylene, a raw material for polyolefin laminates, and found that a packaging product having a polyolefin laminate with a biomass polyolefin resin layer made from biomass-derived ethylene instead of conventional ethylene obtained from fossil fuels is comparable in terms of physical properties, such as mechanical properties, to a packaging product having a polyolefin resin layer manufactured using conventional ethylene obtained from fossil fuels. The present invention is based on this finding.

[0008] Therefore, the object of the present invention is to provide a packaging product comprising a laminate having a paper substrate and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing carbon-neutral polyethylene using biomass-derived ethylene, and to provide a packaging product comprising a laminate having a biomass polyolefin resin layer that is comparable in terms of physical properties such as mechanical properties to a conventional packaging product having a resin layer manufactured from raw materials obtained from fossil fuels. [Means for solving the problem]

[0009] In other words, according to one aspect of the present invention, A packaging product comprising a laminate (excluding the original web A for laminated tubes described below), The laminate comprises: a paper base material (excluding synthetic paper composed of natural pulp and polyethylene pulp), and a biomass polyolefin resin layer made of a biomass polyolefin resin composition that comprises a biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene, and a fossil fuel-derived polyolefin, the biomass polyolefin resin layer being located on one surface side of the paper base material, wherein the paper base material and the biomass polyolefin resin layer are in contact with each other, the packaging product is a laminated tube, thereby providing the packaging product. (Original web A for laminated tubes: an original web for laminated tubes, comprising a metal foil, a low-density polyethylene film or linear low-density polyethylene film adhered to one side of the metal foil, a paper having a low-density polyethylene film or linear low-density polyethylene film disposed on both sides thereof and adhered to the other side of the metal foil, and a longitudinally uniaxially rolled multilayer film laminated on the paper.) In an aspect of the present invention, it is preferable that the biomass polyolefin resin layer comprises biomass-derived low-density polyethylene, and / or biomass-derived linear low-density polyethylene. In an aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains the biomass-derived ethylene in an amount of 5% by mass or more relative to the entire biomass polyolefin resin layer. In an aspect of the present invention, it is preferable to further comprise a barrier layer containing an inorganic substance. In an aspect of the present invention, it is preferable to have a polyethylene resin layer located on the other surface side of the paper base material. [Effects of the Invention]

[0010] The packaging product according to the present invention comprises a laminate having a paper base material and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing biomass-derived polyethylene obtained by polymerizing monomers including biomass-derived ethylene. This makes it possible to realize a packaging product having a carbon-neutral polyolefin resin layer. Therefore, the amount of fossil fuels used can be significantly reduced compared to conventional products, thereby reducing the environmental burden. Furthermore, the packaging product according to the present invention is comparable in terms of physical properties such as mechanical properties to conventional packaging products having a polyolefin resin layer manufactured from raw materials obtained from fossil fuels, and can therefore replace conventional packaging products having a polyolefin resin layer. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic cross-sectional view showing an example of a laminate according to the present invention. [Figure 2] This is a schematic cross-sectional view showing an example of a laminate according to the present invention. [Modes for carrying out the invention]

[0012] In the present invention, "biomass polyolefin resin composition" and "biomass polyolefin resin layer" refer to materials that use biomass-derived raw materials in at least part of their composition, but do not mean that all of the raw materials are biomass-derived.

[0013] Laminate The laminate according to the present invention comprises a paperboard substrate and a biomass polyolefin resin layer. By having a biomass polyolefin resin layer, the laminate can be made a carbon-neutral polyolefin resin laminate. Therefore, the amount of fossil fuels used can be significantly reduced compared to conventional methods, thereby reducing the environmental burden. Furthermore, the laminate according to the present invention is comparable in terms of physical properties, such as mechanical properties, to conventional polyolefin resin laminates manufactured from raw materials obtained from fossil fuels, and can therefore replace conventional polyolefin resin laminates.

[0014] Schematic cross-sectional views of an example of a laminate according to the present invention are shown in Figures 1 and 2. The laminate 10 shown in Figure 1 comprises a paperboard substrate 11 and a biomass polyolefin resin layer 12 formed on the paperboard substrate 11. The laminate 20 shown in Figure 2 comprises a paperboard substrate 21, a first biomass polyolefin resin layer 22 formed on the paperboard substrate 21, and a second biomass polyolefin resin layer 23 formed on the first biomass polyolefin resin layer 22, in this order. The individual layers constituting the laminate will be described below.

[0015] Paperboard substrate In this invention, the paperboard substrate functions as a substrate layer and must have sufficient strength to withstand the process of laminating the biomass polyolefin resin layer by extrusion molding. The paper used as the paperboard substrate has a weight of 100 to 700 g / m². 2 Preferably 150-600 g / m² 2 , comfortable 200~500g / m 2 It has the following basis weight. As the paperboard base material, all types of white paperboard are acceptable, but from a safety standpoint, the use of ivory paper, milk carton paper, cup paper, etc. made from natural pulp is particularly preferred.

[0016] Furthermore, the paperboard used in this invention may use neutral rosin, alkyl ketene dimer, or alkenyl succinic anhydride as a sizing agent, and cationic polyacrylamide or cationic starch as a fixing agent. It is also possible to manufacture the paper in a neutral pH range of 6 to 9 using aluminum sulfate. In addition to the sizing agents mentioned above, the paperboard may also contain various papermaking fillers, yield enhancers, dry strength enhancers, wet strength enhancers, binders, dispersants, flocculants, plasticizers, and adhesives as needed.

[0017] Biomass polyolefin resin layer In the present invention, the biomass polyolefin resin layer contains, preferably 5% by mass or more, more preferably 5 to 95% by mass, and even more preferably 25 to 75% by mass, of the biomass-derived ethylene described below, relative to the entire biomass polyolefin resin layer. The biomass polyolefin resin layer may consist of at least two layers, for example, a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in that order from the paperboard substrate side. The seal layer and core layer of the laminate may both be biomass polyolefin resin layers, or only one of them may be a biomass polyolefin resin layer.

[0018] First biomass polyolefin resin layer In the present invention, the first biomass polyolefin resin layer may function as the core layer of the laminate. Having a core layer allows the laminate to resist breakage and exhibit excellent flexibility.

[0019] The first biomass polyolefin resin layer contains biomass-derived ethylene in an amount of preferably 5% by mass or more, more preferably 5 to 95% by mass, even more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass, relative to the entire first biomass polyolefin resin layer. If the concentration of biomass-derived ethylene in the first biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuels used can be reduced compared to conventional methods, and a carbon-neutral polyolefin resin laminate can be realized.

[0020] The first biomass polyolefin resin layer preferably contains 0.915 to 0.96 g / cm³ 3 , more preferably 0.92~0.955 g / cm³ 3 More preferably 0.93 to 0.955 g / cm³ 3 The density of the first biomass polyolefin resin layer is the value measured according to the method specified in Method A of JIS K7112-1980 after annealing as described in JIS K6760-1995. 3 If the above is true, the rigidity of the first biomass polyolefin resin layer can be increased. Also, if the density of the first biomass polyolefin resin layer is 0.96 g / cm³ 3 The transparency and mechanical strength of the first biomass polyolefin resin layer can be improved if the following conditions are met.

[0021] The first biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g / 10 min, preferably 3 to 25 g / 10 min, and more preferably 4 to 20 g / 10 min. The melt flow rate is a value measured by Method A under the conditions of a temperature of 190°C and a load of 21.18 N in the method specified in JIS K7210-1995. When the MFR of the first biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during molding processing can be reduced. Moreover, when the MFR of the biomass polyolefin resin composition is 30 g / 10 min or less, the mechanical strength of the first biomass polyolefin resin layer can be enhanced.

[0022] The first biomass polyolefin resin layer has a thickness of 10 to 100 μm, preferably 10 to 50 μm, and more preferably 15 to 30 μm.

[0023] Second biomass polyolefin resin layer In the present invention, the second biomass polyolefin resin layer may function as a seal layer of the laminate. By having the heat seal layer, the laminate can be firmly adhered to another resin film without using an adhesive or the like when laminated thereon.

[0024] The second biomass polyolefin resin layer contains biomass-derived ethylene in an amount of preferably 5 mass% or more, more preferably 5 to 95 mass%, and even more preferably 25 to 75 mass%, based on the entire second biomass polyolefin resin layer. When the concentration of the biomass-derived ethylene in the second biomass polyolefin resin layer is 5 mass% or more, the usage amount of fossil fuel can be reduced compared to the conventional art, and a carbon-neutral polyolefin laminate can be realized.

[0025] The second biomass polyolefin resin layer has a density of 0.90 to 0.925 g / cm 3 , preferably 0.905 to 0.925 g / cm 3The density of the second biomass polyolefin resin layer is the value measured according to the method specified in Method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. The density of the second biomass polyolefin resin layer is 0.90 g / cm³. 3 If the above is true, the rigidity of the second biomass polyolefin resin layer can be increased. Also, if the density of the second biomass polyolefin resin layer is 0.925 g / cm³ 3 The transparency and mechanical strength of the second biomass polyolefin resin layer can be improved if the following conditions are met.

[0026] The second biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g / 10 min, preferably 3 to 25 g / 10 min, and more preferably 4 to 20 g / 10 min. The melt flow rate is a value measured by Method A under the conditions of a temperature of 190°C and a load of 21.18 N, as specified in JIS K7210-1995. If the MFR of the second biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during molding can be reduced. Furthermore, if the MFR of the biomass polyolefin resin composition is 30 g / 10 min or less, the mechanical strength of the second biomass polyolefin resin layer can be increased.

[0027] The second biomass polyolefin resin layer has a thickness of 1 to 50 μm, preferably 1 to 20 μm, and more preferably 1 to 10 μm.

[0028] In the present invention, it is preferable that the first biomass polyolefin resin layer and the second biomass polyolefin resin layer satisfy the following specific relationships with respect to density, thickness, MFR, and biomass content (ethylene concentration derived from biomass).

[0029] In the present invention, it is preferable that the density d1 of the first biomass polyolefin resin layer and the density d2 of the second biomass polyolefin resin layer satisfy d1 > d2. This is because the first biomass polyolefin resin layer functions as a core layer and therefore requires rigidity, while the second biomass polyolefin resin layer functions as a heat seal layer and therefore requires flexibility.

[0030] In the present invention, it is preferable that the thickness t1 of the first biomass polyolefin resin layer and the thickness t2 of the second biomass polyolefin resin layer satisfy t1 > t2. This is because the first biomass polyolefin resin layer functions as a core layer and therefore requires a certain thickness, while the second biomass polyolefin resin layer functions as a heat seal layer and therefore does not require the same thickness as the core layer.

[0031] In the present invention, it is preferable that the MFR1 of the first biomass polyolefin resin layer and the MFR2 of the second biomass polyolefin resin layer satisfy the condition MFR1 > MFR2. This is because the first biomass polyolefin resin layer functions as a core layer and therefore requires rigidity, while the second biomass polyolefin resin layer functions as a heat seal layer and therefore requires flexibility.

[0032] In the present invention, it is preferable that the biomass-derived ethylene concentration C1 of the first biomass polyolefin resin layer and the biomass-derived ethylene concentration C2 of the second biomass polyolefin resin layer satisfy the condition C1 > C2. This is because the first biomass polyolefin resin layer functions as a core layer, and therefore has a large thickness and uses a large amount of ethylene. Increasing the biomass content of the first biomass polyolefin resin layer can further reduce the amount of fossil fuels used.

[0033] Biomass-derived ethylene In the present invention, the method for producing biomass-derived ethylene, which is a raw material for biomass-derived polyolefins, is not particularly limited and can be obtained by conventionally known methods. An example of a method for producing biomass-derived ethylene is described below.

[0034] Biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use biomass-derived fermented ethanol obtained from plant materials. The plant materials are not particularly limited, and conventionally known plants can be used. Examples include corn, sugarcane, beets, and manioc.

[0035] In the present invention, biomass-derived fermented ethanol refers to ethanol produced by contacting a culture medium containing a carbon source obtained from plant raw materials with a microorganism that produces ethanol or a product derived from its crushed material, and then purifying it. Conventional known methods such as distillation, membrane separation, and extraction can be applied to purify the ethanol from the culture medium. For example, methods such as adding benzene, cyclohexane, etc. and azeotropic distillation, or removing water by membrane separation, etc., can be used.

[0036] To obtain the ethylene of the present invention, further advanced purification may be performed at this stage, such as reducing the total amount of impurities in the ethanol to 1 ppm or less.

[0037] A catalyst is usually used when obtaining ethylene by the dehydration reaction of ethanol, but this catalyst is not particularly limited, and conventionally known catalysts can be used. A fixed-bed flow reaction is advantageous in terms of process, as it allows for easy separation of the catalyst and product, and for example, γ-alumina is preferred.

[0038] Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. The heating temperature is not limited as long as the reaction proceeds at a commercially useful rate, but a temperature of 100°C or higher is preferable, more preferably 250°C or higher, and even more preferably 300°C or higher. There is no particular upper limit, but from the viewpoint of energy balance and equipment, it is preferable to have a temperature of 500°C or lower, more preferably 400°C or lower.

[0039] The reaction pressure is not particularly limited, but a pressure above atmospheric pressure is preferred to facilitate subsequent gas-liquid separation. Industrially, a fixed-bed flow reaction is preferred because it facilitates catalyst separation, but a liquid-phase suspension bed, fluidized bed, etc., may also be used.

[0040] In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in the ethanol supplied as a raw material. Generally, when performing a dehydration reaction, it is preferable to have no water present in order to improve the efficiency of water removal. However, in the case of the dehydration reaction of ethanol using a solid catalyst, it has been found that the amount of other olefins, especially butene, tends to increase when water is not present. This is probably because the dimerization of ethylene after dehydration cannot be suppressed without the presence of a small amount of water. The lower limit of the acceptable water content is 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but from the viewpoint of mass balance and heat balance, it is preferably 50% by mass or less, more preferably 30% or less, and even more preferably 20% or less.

[0041] By carrying out the dehydration reaction of ethanol in this manner, a mixture of ethylene, water, and a small amount of unreacted ethanol is obtained. However, since ethylene is a gas at room temperature and below approximately 5 MPa, water and ethanol can be removed from this mixture by gas-liquid separation to obtain ethylene. This method can be carried out using known methods.

[0042] The ethylene obtained by gas-liquid separation is further distilled, and there are no particular restrictions on the distillation method, operating temperature, residence time, etc., except that the operating pressure at this time is above atmospheric pressure.

[0043] When the raw material is biomass-derived ethanol, the resulting ethylene contains trace amounts of impurities introduced during the ethanol fermentation process, such as carbonyl compounds like ketones, aldehydes, and esters, as well as their decomposition products like carbon dioxide, and nitrogen-containing compounds like amines and amino acids, as well as their decomposition products like ammonia, which are enzyme decomposition products and contaminants. Depending on the application of the ethylene, these trace amounts of impurities may be problematic and may be removed by purification. The purification method is not particularly limited and can be carried out by conventionally known methods. A suitable purification method is, for example, adsorption purification. The adsorbent used is not particularly limited and can be any conventionally known adsorbent. For example, a material with a high surface area is preferred, and the type of adsorbent is selected according to the type and amount of impurities in the ethylene obtained by the dehydration reaction of biomass-derived ethanol.

[0044] Furthermore, a caustic water treatment may be used in combination as a method for purifying impurities in ethylene. If caustic water treatment is used, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform a water removal treatment after the caustic treatment and before adsorption purification.

[0045] Biomass polyolefins In the present invention, the biomass-derived polyolefin is obtained by polymerizing monomers containing biomass-derived ethylene. It is preferable to use biomass-derived ethylene obtained by the above-described manufacturing method. Since biomass-derived ethylene is used as the raw material monomer, the resulting polyolefin is biomass-derived. Note that the raw material monomer for the polyolefin does not necessarily have to contain 100% by mass of biomass-derived ethylene.

[0046] The monomers used as raw materials for biomass-derived polyolefins may further contain ethylene and / or α-olefins derived from fossil fuels, or further contain α-olefins derived from biomass.

[0047] The above-mentioned α-olefin is not particularly limited in terms of the number of carbon atoms, but typically those with 3 to 20 carbon atoms can be used, and butylene, hexene, or octene are preferred. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a biomass-derived raw material. Furthermore, by including such an α-olefin, the polymerized polyolefin has alkyl groups as branched structures, making it more flexible than simple linear polyolefins.

[0048] The polyolefin mentioned above is preferably polyethylene. This is because, by using ethylene, a biomass-derived raw material, it is theoretically possible to manufacture the product using 100% biomass-derived components.

[0049] The biomass-derived ethylene concentration in the polyolefins mentioned above (hereinafter sometimes referred to as "biomass content") is a value measured by radiocarbon (C14) measurement of the biomass-derived carbon content. Since atmospheric carbon dioxide contains a certain proportion (105.5 pMC) of C14, it is known that the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in the total carbon atoms in the polyolefin, the proportion of biomass-derived carbon can be calculated. In this invention, the C14 content in the polyolefin is P C14 In that case, the carbon content P from biomass bio This can be calculated as follows: P bio (%)=P C14 / 105.5×100

[0050] In this invention, theoretically, if all biomass-derived ethylene is used as the raw material for polyolefins, the biomass-derived ethylene concentration will be 100%, and the biomass content of the biomass-derived polyolefin will be 100%. Furthermore, the biomass-derived ethylene concentration in fossil fuel-derived polyolefins produced solely from fossil fuel-derived raw materials will be 0%, and the biomass content of the fossil fuel-derived polyolefin will be 0%.

[0051] In this invention, the biomass-derived polyolefin and biomass-derived resin layer do not need to be 100% biomass. This is because even if only a part of the laminate is made from biomass-derived raw materials, it is in line with the purpose of this invention, which is to reduce the amount of fossil fuels used compared to conventional methods.

[0052] In the present invention, the polymerization method for monomers containing biomass-derived ethylene is not particularly limited and can be carried out by conventionally known methods. The polymerization temperature and polymerization pressure should be appropriately adjusted depending on the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited and can be conventionally known apparatus. An example of a polymerization method for monomers containing ethylene is described below.

[0053] The polymerization method for polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, can be appropriately selected depending on the type of polyethylene to be polymerized, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE), depending on differences in density and branching. For example, it is preferable to use a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as the polymerization catalyst, and to carry out the polymerization in one or more stages using one of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, or high-pressure ionic polymerization.

[0054] The single-site catalyst described above is a catalyst capable of forming a uniform active species, and is usually prepared by contacting a metallocene transition metal compound or a non-metallocene transition metal compound with an activation co-catalyst. Single-site catalysts are preferred over multi-site catalysts because they have a more uniform active site structure, allowing for the polymerization of polymers with high molecular weight and high uniformity. As a single-site catalyst, metallocene catalysts are particularly preferred. A metallocene catalyst is a catalyst comprising a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a co-catalyst, an organometallic compound if necessary, and each catalytic component of a support.

[0055] In the transition metal compounds of Group IV of the periodic table containing the ligand having the cyclopentadienyl skeleton described above, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, etc. The substituted cyclopentadienyl group has at least one substituent selected from hydrocarbon groups having 1 to 30 carbon atoms, silyl groups, silyl-substituted alkyl groups, silyl-substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups, halosilyl groups, etc. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may bond to each other to form a ring, forming an indenyl ring, a fluorenyl ring, an azlenyl ring, or a hydrogenated version thereof. The ring formed by the bonding of substituents may further have substituents on each other.

[0056] In a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, and hafnium, with zirconium and hafnium being particularly preferred. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and it is preferable that each ligand having a cyclopentadienyl skeleton is bonded to each other by a bridging group. Examples of bridging groups include alkylene groups having 1 to 4 carbon atoms, silylene groups, substituted silylene groups such as dialkylsilylene groups and diarylsilylene groups, and substituted germylene groups such as dialkylgermylene groups and diarylgermylene groups. A substituted silylene group is preferred.

[0057] In transition metal compounds of Group IV of the periodic table, typical ligands other than those having a cyclopentadienyl skeleton include hydrogen, hydrocarbon groups having 1 to 20 carbon atoms (alkyl groups, alkenyl groups, aryl groups, alkylaryl groups, aralkyl groups, polyenyl groups, etc.), halogens, metaalkyl groups, and metaaryl groups.

[0058] The transition metal compounds of Group IV of the periodic table containing the ligand having the cyclopentadienyl skeleton described above can be used as catalyst components, either individually or as a mixture of two or more.

[0059] Co-catalysts are those that can effectively utilize the transition metal compounds of Group IV of the periodic table mentioned above as polymerization catalysts, or that can balance the ionic charge of the catalytically activated state. Examples of co-catalysts include benzene-soluble aluminoxanes and benzene-insoluble organoaluminum oxy compounds, ion-exchangeable layered silicates, boron compounds, ionic compounds consisting of cations containing or not containing active hydrogen groups and non-coordinating anions, lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing fluoro groups.

[0060] Transition metal compounds of Group IV of the periodic table containing ligands having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic compound. The support is preferably a porous oxide of an inorganic or organic compound, and specifically includes ion-exchangeable layered silicates such as montmorillonite, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or mixtures thereof.

[0061] Further organometallic compounds that may be used as needed include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organoaluminum compounds are preferred.

[0062] Furthermore, as the polyolefin, ethylene polymers or copolymers of ethylene and α-olefins may be used individually or in combination of two or more types.

[0063] Biomass polyolefin resin composition In the present invention, the biomass polyolefin resin composition mainly contains the above-mentioned polyolefin. The biomass polyolefin resin composition preferably contains 5% by mass or more, more preferably 5 to 95% by mass, and even more preferably 25 to 75% by mass of biomass-derived ethylene relative to the entire biomass polyolefin resin composition. If the concentration of biomass-derived ethylene in the biomass polyolefin resin composition is 5% by mass or more, the amount of fossil fuels used can be reduced compared to conventional methods, and a carbon-neutral polyolefin laminate can be realized.

[0064] The biomass polyolefin resin composition may contain two or more polyolefins with different biomass concentrations, and the concentration of biomass-derived ethylene in the biomass polyolefin resin composition as a whole should be within the above range.

[0065] The biomass polyolefin resin composition may further contain fossil fuel-derived polyolefins, which are obtained by polymerizing ethylene derived from fossil fuels and monomers containing ethylene and / or α-olefins derived from fossil fuels. In other words, in the present invention, the biomass polyolefin resin composition may be a mixture of biomass-derived polyolefins and fossil fuel-derived polyolefins. The mixing method is not particularly limited and can be mixed by conventionally known methods. For example, it may be a dry blend or a melt blend.

[0066] According to an aspect of the present invention, the biomass polyolefin resin composition preferably contains 5 to 90% by mass, more preferably 25 to 75% by mass, of biomass-derived polyolefin and preferably 10 to 95% by mass, more preferably 25 to 75% by mass, of fossil fuel-derived polyolefin. Even when using such a mixed biomass polyolefin resin composition, it is sufficient that the concentration of biomass-derived ethylene in the biomass polyolefin resin composition as a whole is within the above range.

[0067] In the manufacturing process of the biomass polyolefin resin composition described above, or in the manufactured biomass polyolefin resin composition, various additives may be added in addition to the main component polyolefin, to the extent that their properties are not impaired. Examples of additives include plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weather-resistant agents, antistatic agents, thread friction reducers, slip agents, mold release agents, antioxidants, ion exchange agents, and coloring pigments. These additives are added to the entire biomass polyolefin resin composition in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass.

[0068] Non-biomass polyolefin resin layer The laminate according to the present invention may further have a non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer is a resin layer made of a resin material containing raw materials derived from fossil fuels, and has a biomass content of 0%. If only one of the core layer and the seal layer of the laminate is a biomass polyolefin resin layer, the other may be a non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer can be formed using conventionally known raw materials, and its composition and formation method are not particularly limited. By further having a non-biomass polyolefin resin layer in the laminate, heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties can be imparted or improved. The laminate may have two or more non-biomass polyolefin resin layers. When there are two or more non-biomass polyolefin resin layers, each may have the same composition or different compositions.

[0069] As the non-biomass polyolefin resin layer, for example, resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, or ionomer can be used. These resins may be formed by an extrusion lamination method, or they may be laminated with a heat-resistant substrate layer by dry lamination or extrusion lamination as a film that has been previously manufactured by a T-die method or inflation method.

[0070] Furthermore, the film may be any of the following: stretched polyethylene terephthalate film, silica-deposited stretched polyethylene terephthalate film, alumina-deposited stretched polyethylene terephthalate film, stretched nylon film, silica-deposited stretched nylon film, alumina-deposited stretched nylon film, stretched polypropylene film, polyvinyl alcohol-coated stretched polypropylene film, nylon 6 / metaxylylenediamine nylon 6 co-extruded co-stretched film, or polypropylene / ethylene-vinyl alcohol copolymer co-extruded co-stretched film, or a composite film made by laminating two or more of these films.

[0071] Barrier layer The laminate according to the present invention may further have a barrier layer. The barrier layer is made of an inorganic substance and / or an inorganic oxide, and is preferably made of a vapor-deposited film of an inorganic substance or an inorganic oxide, or a metal foil. The vapor-deposited film can be formed using conventionally known inorganic substances or inorganic oxides by conventionally known methods, and its composition and formation method are not particularly limited. By further having a barrier layer, the laminate can be given or improved gas barrier properties that prevent the transmission of oxygen gas and water vapor, and light-shielding properties that prevent the transmission of visible light and ultraviolet rays. The laminate may have two or more barrier layers. When there are two or more barrier layers, each may have the same composition or different compositions.

[0072] As the vapor-deposited film, for example, a vapor-deposited film of an inorganic substance or inorganic oxide such as silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), or yttrium (Y) can be used. In particular, for packaging materials (bags), a vapor-deposited film of aluminum metal, or a vapor-deposited film of silicon oxide, aluminum metal, or aluminum oxide is preferable.

[0073] Inorganic oxides are written as, for example, SiO X AlOX MO X (In the formula, M represents an inorganic element, and the value of X varies depending on the inorganic element.) The range of X values ​​is as follows: silicon (Si) is 0-2, aluminum (Al) is 0-1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, sodium (Na) is 0-0.5, boron (B) is 0-1.5, titanium (Ti) is 0-2, lead (Pb) is 0-1, zirconium (Zr) is 0-2, and yttrium (Y) is 0-1.5. In the above, when X=0, it is a complete inorganic element (pure substance), which is not transparent, and the upper limit of the range of X is the value when it is completely oxidized. For packaging materials, silicon (Si) and aluminum (Al) are preferably used, with silicon (Si) having a value in the range of 1.0 to 2.0 and aluminum (Al) having a value in the range of 0.5 to 1.5.

[0074] In the present invention, the thickness of the vapor-deposited inorganic material or inorganic oxide film varies depending on the type of inorganic material or inorganic oxide used, but it is desirable to arbitrarily select and form a thickness of approximately 50 to 2000 Å, preferably 100 to 1000 Å. More specifically, in the case of a vapor-deposited aluminum film, a thickness of approximately 50 to 600 Å, more preferably 100 to 450 Å, is desirable, and in the case of a vapor-deposited aluminum oxide or silicon oxide film, a thickness of approximately 50 to 500 Å, more preferably 100 to 300 Å, is desirable.

[0075] Examples of methods for forming deposited films include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, or chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition.

[0076] In other embodiments, the barrier layer may be a metal foil obtained by rolling a metal. Conventional known metal foils can be used as the metal foil. Aluminum foil is preferred from the viewpoint of gas barrier properties that prevent the transmission of oxygen gas and water vapor, and light shielding properties that prevent the transmission of visible light and ultraviolet rays.

[0077] Other layers The laminate according to the present invention may have at least one additional layer besides the layers described above. If there are two or more additional layers, each may have the same composition or different compositions. The additional layers can be formed on any one or more of the above layers. Examples of additional layers include a printed layer and an adhesive layer. The printed layer can be formed using conventionally known pigments or dyes, and the method of formation is not particularly limited. The adhesive layer is an adhesive layer or adhesive resin layer formed to bond any two layers by lamination. As the laminating adhesive, for example, a one-component or two-component curing or non-curing type vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, etc., solvent-based, water-based, or emulsion-type laminating adhesive can be used. As a coating method for the above adhesive, for example, it can be applied by direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, fontein method, transfer roll coating, or other methods. The application rate is 0.1 g / m². 2 ~10g / m 2 (Dry state) is preferable, 1 g / m 2 ~5g / m 2 A (dry) state is preferable.

[0078] Furthermore, a resin layer consisting of a thermoplastic resin layer is used as the adhesive resin layer. Specifically, as the material for the adhesive resin layer, low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, copolymer resin of ethylene-α-olefin polymerized using a metallocene catalyst, ethylene-polypropylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methacrylic acid copolymer resin, ethylene-methyl methacrylate copolymer resin, ethylene-maleic acid copolymer resin, ionomer resin, resin obtained by graft polymerization or copolymerization of unsaturated carboxylic acids, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, or ester monomers onto polyolefin resin, and resin obtained by graft-modifying maleic anhydride onto polyolefin resin can be used. One or more of these materials can be used in combination.

[0079] The method for manufacturing the laminate according to the present invention is not particularly limited and can be manufactured by conventionally known methods. In the present invention, it is preferable to form a biomass polyolefin resin layer on a paper substrate by extrusion molding, and it is more preferable that the biomass polyolefin resin layer is formed by co-extrusion molding. It is even more preferable that the co-extrusion molding is carried out by the T-die method or the inflation method.

[0080] For example, a laminate can be formed by extrusion molding using the following method. After drying the biomass polyolefin resin composition described above, it is supplied to a melt extruder heated to a temperature above the melting point of polyolefin (Tm) to Tm+70°C to melt the biomass polyolefin resin composition, extrude it into a sheet on a paper substrate using a die such as a T-die, and rapidly cool and solidify the extruded sheet in a rotating cooling drum or the like to form a laminate. As the melt extruder, a single-screw extruder, twin-screw extruder, vented extruder, tandem extruder, etc., can be used depending on the purpose.

[0081] The thickness of the laminate obtained as described above can be arbitrary depending on its application, but is usually about 5 to 500 μm, preferably about 20 to 300 μm.

[0082] The laminate according to the present invention can be subjected to secondary processing for the purpose of imparting chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, biocompatibility, and other surface functions. Examples of secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, and surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Furthermore, molded products can be manufactured by applying lamination (dry lamination or extrusion lamination), bag making, and other post-processing processes to the laminate according to the present invention.

[0083] Purpose The laminate according to the present invention can be suitably used for various applications such as packaging products like packaging containers and packaging bags, sheet molded products like decorative sheets and trays, laminated films, optical films, resin plates, various label materials, lid materials, and laminate tubes, with packaging products being particularly preferred.

[0084] <Other forms> The present invention provides a packaging product comprising a laminate having a paperboard substrate and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing carbon-neutral polyethylene using biomass-derived ethylene, and also aims to provide a packaging product comprising a laminate having a biomass polyolefin resin layer that is comparable in terms of physical properties such as mechanical properties to a conventional packaging product having a resin layer manufactured from raw materials obtained from fossil fuels. According to another aspect of the present invention, A packaging product comprising a laminate (excluding the raw material A for laminate tubes described below), The laminated body is Paperboard substrate and The cardboard substrate has a biomass polyolefin resin layer located on one side, which is made of a biomass polyolefin resin composition comprising biomass-derived polyethylene formed by polymerizing monomers containing biomass-derived ethylene and fossil fuel-derived polyolefin. A packaging product is provided in which the aforementioned packaging product is a laminated tube. (Laminate tube raw material A: A raw material for a laminate tube comprising a metal foil, a low-density polyethylene film or linear low-density polyethylene film adhered to one side of the metal foil, paper adhered to the other side of the metal foil, with low-density polyethylene film or linear low-density polyethylene film arranged on both sides thereof, and a longitudinally uniaxially rolled multilayer film laminated on the paper.) According to yet another aspect of the present invention, A packaging product comprising a laminate, The laminated body is Paperboard substrate and The cardboard substrate has a biomass polyolefin resin layer located on one side, which is made of a biomass polyolefin resin composition comprising biomass-derived polyethylene formed by polymerizing monomers containing biomass-derived ethylene and fossil fuel-derived polyolefin. A packaging product is provided in which the aforementioned packaging product is a lid material (excluding lid material B below). (Lid material B: A lid material for a food container, comprising a laminated sheet having two waterproof layers and a base layer made of paper disposed between the two waterproof layers, wherein at least one of the two waterproof layers is an aluminum layer made of aluminum foil.) In another embodiment of the present invention, it is preferable that the biomass polyolefin resin layer comprises biomass-derived low-density polyethylene and / or biomass-derived linear low-density polyethylene. In another embodiment of the present invention, it is preferable that the biomass polyolefin resin layer contains 5% by mass or more of biomass-derived ethylene relative to the entire biomass polyolefin resin layer. In another embodiment of the present invention, it is preferable to further have a barrier layer containing an inorganic material. In another embodiment of the present invention, it is preferable to have a polyethylene resin layer located on the other side of the paperboard substrate. Another aspect of the present invention provides a packaging product comprising a laminate having a paperboard substrate and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing biomass-derived polyethylene obtained by polymerizing monomers including biomass-derived ethylene. This enables the realization of a packaging product having a carbon-neutral polyolefin resin layer. Therefore, the amount of fossil fuels used can be significantly reduced compared to conventional methods, thereby reducing the environmental burden. Furthermore, the packaging product according to the present invention is comparable in terms of physical properties, such as mechanical properties, to conventional packaging products having a polyolefin resin layer manufactured from raw materials obtained from fossil fuels, and can therefore replace conventional packaging products having a polyolefin resin layer. The present invention provides a laminate comprising a paperboard substrate and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing a carbon-neutral polyolefin using biomass-derived ethylene, and also aims to provide a biomass polyolefin resin laminate that is comparable in terms of physical properties such as mechanical properties to conventional laminates having a resin layer manufactured from raw materials obtained from fossil fuels. According to further other embodiments of the present invention, 100-700g / m 2 A paperboard substrate having the basis weight, A biomass polyolefin resin layer comprising a biomass polyolefin resin composition containing a biomass-derived polyolefin obtained by polymerizing monomers including biomass-derived ethylene, and A laminate having the following is provided. In yet another embodiment of the present invention, it is preferable that the biomass polyolefin resin layer contains 5% by mass or more of biomass-derived ethylene relative to the entire biomass polyolefin resin layer. In yet another embodiment of the present invention, the biomass polyolefin resin layer preferably comprises a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in that order from the paperboard substrate side, wherein the first biomass polyolefin resin layer contains 5% by mass or more of biomass-derived ethylene relative to the entire first biomass polyolefin resin layer, and the second biomass polyolefin resin layer preferably contains 5% by mass or more of biomass-derived ethylene relative to the entire second biomass polyolefin resin layer. In yet another embodiment of the present invention, it is preferable that the biomass-derived ethylene concentration C1 in the first biomass polyolefin resin layer and the biomass-derived ethylene concentration C2 in the second biomass polyolefin resin layer satisfy C1 > C2. In yet another embodiment of the present invention, the monomer may further comprise ethylene and / or α-olefins derived from fossil fuels. In yet another embodiment of the present invention, the monomer may further comprise a biomass-derived α-olefin. In yet another embodiment of the present invention, the biomass polyolefin resin composition may further comprise a fossil fuel-derived polyolefin obtained by polymerizing ethylene derived from fossil fuels and monomers containing ethylene and / or α-olefins derived from fossil fuels. In yet another embodiment of the present invention, the biomass polyolefin resin composition may contain 5 to 90% by mass of the biomass-derived polyolefin and 10 to 95% by mass of the fossil fuel-derived polyolefin. In yet another embodiment of the present invention, the α-olefin is preferably butylene, hexene, or octene. In yet another embodiment of the present invention, the polyolefin is preferably polyethylene. In yet another embodiment of the present invention, the laminate may further comprise a non-biomass polyolefin resin layer made of a resin material containing raw materials derived from fossil fuels. In yet another embodiment of the present invention, the laminate may further have a barrier layer made of an inorganic material and / or an inorganic oxide. In yet another embodiment of the present invention, it is preferable that the biomass polyolefin resin layer is formed on the paperboard substrate by extrusion molding. In yet another embodiment of the present invention, it is preferable that the biomass polyolefin resin layer is formed by co-extrusion molding. In yet another embodiment of the present invention, the co-extrusion molding is preferably carried out by a T-die method or an inflation method. In yet another embodiment of the present invention, a packaging product comprising the laminate is provided. A laminate according to yet another aspect of the present invention has a paperboard substrate and a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing a biomass-derived polyolefin obtained by polymerizing monomers including biomass-derived ethylene, thereby realizing a carbon-neutral polyolefin resin laminate. Therefore, the amount of fossil fuels used can be significantly reduced compared to conventional methods, thereby reducing the environmental burden. Furthermore, the laminate according to yet another aspect of the present invention is comparable to conventional polyolefin laminates made from raw materials obtained from fossil fuels in terms of physical properties such as mechanical properties, and can therefore replace conventional polyolefin laminates. [Examples]

[0085] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0086] Measurement conditions In the following reference examples, reference comparative examples, examples, and comparative examples, the biomass content refers to the value of the carbon content derived from biomass as determined by radiocarbon (C14) measurement.

[0087] The conditions of the extrusion film-forming machine used below were as follows: Screw diameter: 90mm Screw type: Full flight L / D: 28 T-Die: 11S type straight manifold T-die effective opening length: 560mm

[0088] Example 1 For the body and bottom of the paper cup container, the cardboard base material is acid-resistant paper (Oji Specialty Paper Co., Ltd.: Acid-resistant BYO-500, basis weight 320g / m²). 2 A coronoid was used, and its reverse side was subjected to corona treatment. Next, as the core layer on the paperboard substrate side, a resin was prepared by dry blending fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: LC701, MFR: 14, density: 0.919) and biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL3180, MFR: 2.7, density: 0.918, biomass content: 87%) in a 50:50 ratio. In addition, a fossil fuel-derived low-density polyethylene resin (manufactured by Nippon Polyethylene Co., Ltd.: Novatec LC520, MFR: 3.6, density: 0.923) was prepared as the seal layer. The above resins were co-extruded onto the corona-treated surface of the paperboard substrate at resin temperatures of 290°C and 320°C, respectively (core layer: 20 μm, seal layer: 20 μm), and extruded at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The biomass content of the extruded layer was 22%.

[0089] Example 2 For the body and bottom material of the paper cup container, the cardboard base material is cup paper (manufactured by Nippon Paper Industries Co., Ltd.: basis weight 220g / m²). 2 Using a specific method, corona treatment was performed, and then 55 parts by mass of fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923)) and 45 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass content: 87%) were dry-blended into a resin at a resin temperature of 320°C (25 μm), and the material was extruded and coated at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The biomass content of the extruded layer was 41%.

[0090] Comparative Example 1 For the body and bottom of the paper cup container, the cardboard base material is acid-resistant paper (Oji Specialty Paper Co., Ltd.: Acid-resistant BYO-500, basis weight 320g / m²). 2 Using a material, the reverse side was subjected to corona treatment, and then a low-density polyethylene resin derived from fossil fuels (Novatec LC520, manufactured by Nippon Polyethylene Co., Ltd., MFR: 3.6, density: 0.923) was extruded (40 μm) onto the corona-treated surface at a resin temperature of 320°C and extruded at a line speed of 100 m / min to obtain a non-biomass polyethylene laminate. The biomass content of the extruded layer was 0%.

[0091] Comparative Example 2 For the body and bottom material of the paper cup container, the cardboard base material is cup paper (manufactured by Nippon Paper Industries Co., Ltd.: basis weight 220g / m²). 2 Using a specific material, corona treatment was performed, and then low-density polyethylene (LC520, manufactured by Nippon Polyethylene Co., Ltd., MFR: 3.6, density: 0.923) derived from fossil fuels was extruded (25 μm) onto the corona-treated surface at a resin temperature of 320°C and at a line speed of 100 m / min to obtain a non-biomass polyethylene laminate. The biomass content of the extruded layer was 0%.

[0092] Making paper cups Next, using the laminate manufactured above, a frustoconical blank plate was punched out from the laminate to form the body of the paper cup. Then, the blank plate was rolled into a cylinder, its ends were partially overlapped, and the overlapping portion was framed to heat and melt the low-density polyethylene resin layer present in the overlapping portion. Subsequently, the body was pressed with a hot plate or the like to form a body seal, thereby manufacturing the cylindrical cup body that constitutes the paper cup.

[0093] On the other hand, similarly to the above, the laminate manufactured above was used and punched out in a circular shape to produce a disc that constitutes the bottom, and then the outer circumference of the disc was molded upright into a cylindrical shape to produce a bottom with an upright molded portion. Next, the bottom paper manufactured above was inserted into the cylindrical cup body manufactured above, and then hot air or the like was blown onto the joint between the cylindrical cup body and the bottom paper to heat and melt the resin layer present at the joint. Subsequently, the tip of the cylindrical cup body was bent inward using a curling die and placed over the upright molded portion that constitutes the bottom, and the overlapping portion between the tip of the cylindrical cup body and the upright molded portion of the bottom was knurled from the inner diameter side to tightly bond the cylindrical cup body and the bottom to form a joint, thereby forming a paper cup bottom consisting of a cylindrical cup body and a bottom.

[0094] Subsequently, the bottom of the cylindrical cup body was tightly bonded to form a joint, and the short end opposite to this joint was curled outwards using a curling mold, similar to the method described above, to form an outward-curled upper end, thereby manufacturing a paper cup with a full capacity of 353cc.

[0095] In both Examples 1 and 2 and Comparative Examples 1 and 2, cup molding was successfully performed without any problems. Furthermore, when these paper cups were subjected to destructive testing and visually inspected for any sealing abnormalities, paper peeling was observed in both cases, confirming that sufficient sealing strength was achieved.

[0096] Reference example 1 A non-biomass polyethylene laminate was obtained by co-extruding a PET film as a base material, with the first layer being a dry blend of 50 parts by mass of linear low-density polyethylene (NH745, manufactured by Nippon Polyethylene Co., Ltd., MFR: 8.0, density: 0.913) derived from fossil fuels and 50 parts by mass of linear low-density polyethylene (SLL318, manufactured by Braskem, MFR: 2.7, density: 0.918, biomass content: 87%), and the second layer being LC520, manufactured by Nippon Polyethylene Co., Ltd., MFR: 3.6, density: 0.923, 20μm), both at a resin temperature of 320°C (line speed 100m / min).

[0097] Reference example 2 A non-biomass polyethylene laminate was obtained by co-extruding a PET film as a base material, with the first layer being linear low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd.: NH745 (MFR: 8.0, density: 0.913, 20 μm)) and the second layer being low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923, 20 μm)) at a resin temperature of 300°C (line speed 100 m / min).

[0098] Film evaluation Film samples A and B were obtained by peeling the PET film substrate from the laminates obtained in Reference Example 1 and Reference Example 2, respectively. Each obtained film sample was cut into 15 mm wide and 200 mm long specimens from both the MD and CD directions to form test pieces. The tensile strength and elongation of these test pieces were measured using a tensile testing machine (Tensilon RTC-125A, Orientec Co., Ltd.) under conditions of 23°C and 50 RH% humidity. Furthermore, each film sample was sealed at a temperature of 150°C and a sealing pressure of 30 N / cm². 2 The material was heat-sealed with a sealing time of 1 second, and the seal strength (N / 15mm) was measured using a tensile testing machine (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.).

[0099] The evaluation results are shown in Table 1. No significant differences were observed between film samples A and B in any of the evaluation items. In other words, the biomass resin film (A) was comparable to the non-biomass resin film (B) in terms of physical properties such as mechanical characteristics. [Table 1]

[0100] Example 3 For liquid paper container applications, the paper base material is milk carton paper (manufactured by Clearwater Co., Ltd.: basis weight 320g / m²). 2 Using ), the surface side was flame-treated, and then fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923)) was extruded at a resin temperature of 320°C (20 μm). Subsequently, the back side was also flame-treated, and then, on this flame-treated surface (back side), 50 parts by mass of fossil fuel-derived linear low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: NH745 (MFR: 8.0, density: 0.913) and biomass-derived linear low-density polyethylene were co-extruded as the first layer. A resin (20 μm) was dry-blended with 50 parts by mass of high-density polyethylene (Braskem: SLL318, MFR: 2.7, density: 0.918, biomass content: 87%), and a second layer of fossil fuel-derived low-density polyethylene (Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923, 20 μm) was extruded at a resin temperature of 300°C (line speed 100 m / min) to obtain a biomass polyethylene laminate. The biomass content of the entire laminate excluding the paper base material was 15%.

[0101] Comparative Example 3 The cardboard base material is milk carton paper (manufactured by Clearwater Co., Ltd.: basis weight 320g / m²). 2Using a material, a flame treatment was applied to the surface side, and then fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923)) was extruded at a resin temperature of 320°C (20 μm). Subsequently, a flame treatment was also applied to the back side, and then, on this flame-treated surface (back side), a fossil fuel-derived linear low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: NH745 (MFR: 8.0, density: 0.913, 20 μm)) was co-extruded as the first layer, and a fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923, 20 μm)) was co-extruded as the second layer, both at a resin temperature of 300°C (line speed 100 m / min), to obtain a non-biomass polyethylene laminate.

[0102] Example 4 Primarily used for paper containers of liquids that can be stored at room temperature for extended periods, such as sake, the paper base material is Clearwater Co., Ltd. 400g / m² 2 Low-density polyethylene 20g / m² on the printing surface 2Frame treatment was applied to the unlaminated side of the extruded laminated film. On this framed surface, a film made by dry laminating aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and fossil fuel-derived PET film (Toyobo Co., Ltd.: E5100, 12 μm) (DIC: main agent LX-703A / curing agent KR-90) was laminated by extrusion lamination with ethylene-acrylic acid copolymer (Mitsui DuPont Polychemicals: Nuclel N0908C, 20 μm) and then bonded together. Subsequently, the PET surface of the dry laminate film was coated with a polyester polyol / isocyanate two-component curing anchor agent (Mitsui Takeda Polychemical Co., Ltd.: A3210 / AT3075). Then, 50 parts by mass of fossil fuel-derived low-density polyethylene (Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923)) and 50 parts by mass of biomass-derived linear low-density polyethylene (Braskem Co., Ltd.: SLL318, MFR: 2.7, density: 0.918, biomass content: 87%) were dry-blended, extruded (20 μm) at a resin temperature of 320°C, and laminated with a low-density polyethylene film (Dai Nippon Printing Co., Ltd.: SKL, density: 0.923, 40 μm) at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The biomass content of the entire laminate excluding the paper substrate was 6%.

[0103] Example 5 Primarily used for paper containers of liquids that can be stored at room temperature for extended periods, such as sake, the paper base material is Clearwater Co., Ltd. 400g / m² 2 Low-density polyethylene 20g / m² on the printing surface 2Frame treatment was applied to the unlaminated side of the extruded laminated film. On this framed surface, a film made by dry laminating aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and biomass-derived PET film (Toyobo Co., Ltd.: DE024, 12 μm) (DIC: main agent LX-703A / curing agent KR-90) was laminated by extrusion lamination and bonded together with ethylene-acrylic acid copolymer (Mitsui DuPont Polychemicals: Nuclel N0908C, 20 μm). Subsequently, the PET surface of the dry laminate film was coated with a polyester polyol / isocyanate two-component curing anchor agent (Mitsui Takeda Polychemical Co., Ltd.: A3210 / AT3075). Then, 50 parts by mass of fossil fuel-derived low-density polyethylene (Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923)) and 50 parts by mass of biomass-derived linear low-density polyethylene (Braskem Co., Ltd.: SLL318, MFR: 2.7, density: 0.918, biomass content: 87%) were dry-blended, extruded (20 μm) at a resin temperature of 320°C, and laminated with a low-density polyethylene film (Dai Nippon Printing Co., Ltd.: SKL, density: 0.923, 40 μm) at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The biomass content of the entire laminate excluding the paper substrate was 9%.

[0104] Comparative Example 4 Primarily used for paper containers of liquids that can be stored at room temperature for extended periods, such as sake, the paper base material is Clearwater Co., Ltd. 400g / m² 2 Low-density polyethylene 20g / m² on the printing surface 2Frame treatment was applied to the unlaminated side of the extruded laminated film. On this framed surface, a film made by dry laminating aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and fossil fuel-derived PET film (Toyobo Co., Ltd.: E5100, 12 μm) (DIC: main agent LX-703A / curing agent KR-90) was laminated by extrusion lamination with ethylene-acrylic acid copolymer (Mitsui DuPont Polychemicals: Nuclel N0908C, 20 μm) and then bonded together. Subsequently, a polyester polyol / isocyanate two-component curing anchoring agent (Mitsui Takeda Polychemical Co., Ltd.: A3210 / AT3075) was coated onto the PET surface of the dry laminate film. Then, fossil fuel-derived low-density polyethylene (Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923)) was extruded (20 μm) at a resin temperature of 320°C, and laminated with a low-density polyethylene film (Dai Nippon Printing Co., Ltd.: SKL, density: 0.923, 40 μm) at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The biomass content of the entire laminate excluding the paper substrate was 0%.

[0105] Comparative Example 5 Primarily used for paper containers of liquids that can be stored at room temperature for extended periods, such as sake, the paper base material is Clearwater Co., Ltd. 400g / m² 2 Low-density polyethylene 20g / m² on the printing surface 2An anchor coat of polyethyleneimine was applied to the unlaminated surface of the extruded laminated film. On top of this, a film made by dry laminating aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and biomass-derived PET film (Toyobo Co., Ltd.: DE024, 12 μm) (DIC: main agent LX-703A / curing agent KR-90) was laminated by extrusion onto an ethylene-acrylic acid copolymer (Mitsui DuPont Polychemicals: Nuclel N0908C, 20 μm) and then bonded together. Subsequently, a polyester polyol / isocyanate two-component curing anchoring agent (Mitsui Takeda Polychemical Co., Ltd.: A3210 / AT3075) was coated onto the PET surface of the dry laminate film. Then, fossil fuel-derived low-density polyethylene (Nippon Polyethylene Co., Ltd.: LC520 (MFR: 3.6, density: 0.923)) was extruded (20 μm) at a resin temperature of 320°C, and laminated with a low-density polyethylene film (Dai Nippon Printing Co., Ltd.: SKL, density: 0.923, 40 μm) at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The biomass content of the entire laminate excluding the paper substrate was 3%.

[0106] Container strength evaluation Using the cartons prepared in Example 4 and Comparative Example 4, water was filled and molded using a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd. Afterward, the individual compressive strength of these samples was measured in two directions: vertically and horizontally (with the entire opening facing sideways). As shown in Table 2, no significant difference was observed between the biomass-derived and fossil fuel-derived products. [Table 2]

[0107] Seal performance evaluation (filling machine verification) The cartons prepared in Example 4 and Comparative Example 4 were filled with water and molded using a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd., and the top and bottom sealability was compared. The sealability was evaluated by visual inspection after sealing with permeate according to the following criteria. As shown in Table 3, no significant difference was observed between the biomass-derived product and the fossil fuel-derived product. Seal performance evaluation criteria ○: Good. △: There were no missing stickers, but there was a tendency for them to come off. ×: The sticker was found to be missing. [Table 3] [Explanation of Symbols]

[0108] 10 Laminate 11 Paper base material 12. Biomass polyolefin resin layer 20 Laminate 21 Paperboard substrate 22 First biomass polyolefin resin layer 23. Second biomass polyolefin resin layer

Claims

1. A packaging product comprising a laminate (excluding the raw material A for laminate tubes described below), The laminated body is Paper substrate (excluding synthetic paper made from natural pulp and polyethylene pulp), A biomass polyolefin resin layer is located on one side of the paper substrate and is made of a biomass polyolefin resin composition comprising biomass-derived polyethylene formed by polymerizing monomers containing biomass-derived ethylene and polyolefin derived from fossil fuels. It comprises, in this order, a non-biomass polyolefin resin layer made of resin material containing raw materials derived from fossil fuels, The paper substrate and the biomass polyolefin resin layer are in contact, A packaging product in which the aforementioned packaging product is a laminated tube. (Laminate tube raw material A: A laminate tube raw material comprising a metal foil, a low-density polyethylene film or linear low-density polyethylene film adhered to one side of the metal foil, paper adhered to the other side of the metal foil, with low-density polyethylene film or linear low-density polyethylene film arranged on both sides thereof, and a longitudinally uniaxially rolled multilayer film laminated on the paper.)

2. The packaging product according to claim 1, wherein the biomass polyolefin resin layer comprises biomass-derived low-density polyethylene and / or biomass-derived linear low-density polyethylene.

3. The packaging product according to claim 1 or 2, wherein the biomass polyolefin resin layer contains 5% by mass or more of biomass-derived ethylene relative to the entire biomass polyolefin resin layer.

4. The packaging product according to any one of claims 1 to 3, further comprising a barrier layer containing an inorganic substance.

5. The packaging product according to any one of claims 1 to 4, having a polyethylene resin layer located on the other side of the paper substrate.

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